US4471076A - Process for the preparation of fluorocarbon polymers containing carboxyl groups, and certain starting materials required for this, and the fluoro-sulfato compounds formed as intermediate products in the process - Google Patents

Process for the preparation of fluorocarbon polymers containing carboxyl groups, and certain starting materials required for this, and the fluoro-sulfato compounds formed as intermediate products in the process Download PDF

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US4471076A
US4471076A US06/467,179 US46717983A US4471076A US 4471076 A US4471076 A US 4471076A US 46717983 A US46717983 A US 46717983A US 4471076 A US4471076 A US 4471076A
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groups
chain end
give
crosslinked
end groups
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Peter Blickle
Johannes Brandrup
Hans Millauer
Werner Schwertfeger
G/u/ nter Siegemund
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Hoechst AG
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Hoechst AG
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Assigned to HOECHST AKTIENGESELLSCHAFT, A GERMAN CORP. reassignment HOECHST AKTIENGESELLSCHAFT, A GERMAN CORP. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: BLICKLE, PETER, BRANDRUP, JOHANNES, MILLAUER, HANS, SCHWERTFEGER, WERNER, SIEGEMUND, GUNTER
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages

Definitions

  • the polymers described in that article are prepared by copolymerizing, for example, monomers of the formula ##STR3## with tetrafluoroethylene CF 2 ⁇ CF 2 .
  • the polymers are then extruded and shaped and also subjected to a hydrolytic treatment in order to convert the ester groups into the carboxyl groups (in the free form or in the form of salts).
  • Polymers having --CF 2 --SO 2 F groups in the side chains are then formed by homopolymerizing or copolymerizing these compounds.
  • the --CF 2 --SO 2 F groups can be hydrolyzed to give --CF 2 --SO 3 H groups or can, for example, also undergo a functional change by reduction to give COOH groups.
  • the latter--the functional change of --CF 2 --SO 2 F or --CF 2 --SO 3 H groups into COOH groups-- is known, for example from U.S. Pat. No. 4,267,364.
  • the invention relates, therefore, to a process for the preparation of virtually non-crosslinked fluorocarbon polymers containing carboxyl groups, which comprises the following reaction stages:
  • R is C 1 to C 6 -alkyl, preferably methyl or ethyl), which are saponified to give the free carboxyl groups
  • the process makes it possible to introduce functions into non-crosslinked fluorocarbon polymers containing no functional groups; since the --CHFX end groups of the side chains (X is F or CF 3 ) do not constitute functional groups. Because special and, in some cases, involved measures for preserving the functional groups in a series of stages of a synthesis are avoided, the process constitutes a considerable advance.
  • the starting materials for the process according to the invention -i.e. non-crosslinked fluorocarbon polymers in which the linear macromolecules carry side chains containing the end group --CHFX (X is F or CF 3 )--contain no further H atoms, apart from the H atoms in the said end group; some of them are known polymers, others are new polymers.
  • Preferred non-crosslinked fluorocarbon polymers in which X is CF 3 in the side chain end group are those which are obtained by homopolymerizing or copolymerizing the vinyl ethers of the formula below: ##STR9##
  • the homopolymerization or copolymerization (preferably with CF 2 ⁇ CF 2 ) of these vinyl ethers can be effected by known procedures, such as are, for example, described in German Auslegeschrift No. 1,806,097 and German Offenlegungsschrift No. 2,639,109.
  • the copolymerization can, in particular, be effected by the process described in German Auslegeschrift No. 1,806,097, in a liquid Cl--F-alkane solvent in the presence of a low-temperature initiator, such as, for example, bis-(perfluoropropionyl) peroxide, at temperatures of about 30°-90° C. and low pressures.
  • a low-temperature initiator such as, for example, bis-(perfluoropropionyl) peroxide
  • the copolymerization can, however, also be carried out, preferably as an emulsion polymerization, in an aqueous medium in the presence of emulsifiers and buffer substances and of initiators which form free radicals, as described in German Offenlegungsschrift No. 2,639,109, but it is possible, if desired, to dispense with the chain transfer agent.
  • non-crosslinked starting fluorocarbon polymers which are preferred for the process according to the invention are polymers containing recurring units of the formula (A) ##STR12## in which u is 0,1 or 2,
  • v 0 or 1
  • w 1-7 and
  • X and Y independently of one another are F or CF 3 ,
  • Z is Cl, F, R f or --OR f (R f is CF 3 or a C 2 -C 8 -perfluoroalkyl radical which is optionally interrupted by 0 atoms).
  • u 0 or 1
  • w is 1-5, especially 2-5,
  • Y is CF 3
  • Z is F, CF 3 , --O--CF 2 --CF 2 --CF 3 or ##STR13## in particular only F.
  • the ratio of these structural units to the structural units --CF 2 --CFZ is preferably about 1:(2 to 20), in particular about 1:(2-8).
  • the copolymers of this composition are new compounds. Amongst the latter, preferred copolymers are, in turn, the bipolymers containing units (A) and units --CF 2 --CF 2 -- as (B), and also the terpolymers containing units (A) and, as (B), units --CF 2 --CF 2 -- and --CF 2 --CFZ-- in which Z has the abovementioned meaning excluding F.
  • Copolymers which are particularly preferred are bipolymers containing, in the abovementioned molar ratios, units A and units --CF 2 --CF 2 --, i.e. copolymers of tetrafluoroethylene.
  • the new copolymers are particularly suitable as starting materials for the process according to the invention because they produce, in the end products, the optimum number of carboxyl groups for cation exchangers.
  • reaction stage a which is most fundamental for the process according to the invention: the reaction with peroxodisulfuryl difluoride.
  • the starting fluorocarbon polymer in the form of shaped structures such as, for example, films; if films are employed, a film thickness of about 5 to 300 ⁇ is preferred.
  • an advantageous particle size for the powder is between about 2 and 100 ⁇ , preferably about 5 to 50 ⁇ .
  • Peroxodisulfuryl difluoride can be prepared by known methods, such as, for example, those described by F. B. Dundley in J.Chem.Soc.1963, pages 3407 to 3411. Thus purely chemical methods as well as electrochemical methods are suitable for its preparation.
  • Examples of purely chemical methods are the direct reaction of SO 3 with fluorine using Ag 2 F 2 as catalyst, or the oxidation of metal fluorosulfonates with fluorine.
  • a suitable electrochemical method is, above all, the anodic oxidation of solutions of alkali metal fluorosulfonates in fluorosulfonic acid.
  • the peroxodisulfuryl difluoride prepared by this electrochemical method is also the product which is preferably used for the process according to the invention.
  • In-cell denotes that the polymer to be reacted is present in the electrolyte in the electrochemical cell.
  • Ex-cell on the other hand means that the polymer is present in a second vessel or reactor into which the electrolyte containing peroxide is introduced, for example by circulatory pumping. It is also possible to carry out “ex-cell” reactions in which the polymer and the peroxide are reacted with one another in another diluent after the peroxide has been isolated from the electrolyzed fluorosulfonic acid; examples of diluents of this type are perfluoroalkanes, perfluorinated ethers, N(C 4 F 9 ) 3 and perfluoroalkanes containing fluorosulfato groups.
  • Electrochemical cells in the form of a pot or trough are suitable for carrying out the "in-cell” processes and for preparing the peroxide required for "ex-cell” processes.
  • the electrochemical cells can be divided or undivided cells, the undivided form generally being completely adequate. Against its simpler and cheaper construction must, of course, be set a slightly lower current yield, caused by the cathodic reduction of the peroxodisulfuryl difluoride.
  • the materials which are known for electrochemical production are suitable as the electrode materials.
  • Suitable anode materials are, therefore, platinum and alloys of platinum with the platinum group and/or vitreous carbon; amongst these, a preferred anode material is vitreous carbon.
  • the electrolyte is composed of fluorosulfonic acid in which a salt of fluorosulfonic acid has been dissolved in order to improve its electrical conductivity.
  • the alkali metal fluorosulfonates are particularly preferred conducting salts of this type.
  • Such electrolytes are prepared by processes which are known per se.
  • reaction stage (a) using electrochemically prepared peroxodisulfuryl difluoride in the "in-cell" process by electrolyzing the non-crosslinked starting fluorocarbon polymer containing the side chain end groups --CHFX (X is F or CF 3 ) in an electrolyte composed of fluorosulfonic acid and an alkali metal fluorosulfonate using platinum, alloys of platinum with metals of the platinum group and/or vitreous carbon as anode materials and using cathode materials which are customary, but are stable under the conditions of electrolysis.
  • electrochemically prepared peroxodisulfuryl difluoride in the "in-cell” process by electrolyzing the non-crosslinked starting fluorocarbon polymer containing the side chain end groups --CHFX (X is F or CF 3 ) in an electrolyte composed of fluorosulfonic acid and an alkali metal fluorosulfonate using platinum, alloys of platinum with metals of the platinum group and/or vitr
  • the reaction temperature can be selected within a fairly wide range--between about -10° and about +80° C.; preferably, however, it is between about 5° and about 30° C.
  • the current densities used are generally between about 2 and 200 mA.cm -2 , preferably between about 30 and 100 mA.cm -2 , relative to the anode.
  • the cathode current density is selected at a value about 2 to 30 times as high, which can be achieved by making the surface of the cathode correspondingly smaller. The purpose of this is to repress the diffusion-controlled cathodic reduction of the peroxodisulfuryl difluoride in an undivided cell.
  • Concentration of peroxodisulfuryl difluoride between about 0.1 and about 2.5 moles.1 -1 can be set up in this manner.
  • the highest possible peroxide concentrations are, of course, advantageous for achieving a rapid reaction with the polymer.
  • the peroxide concentration is monitored by methods which are known per se for this purpose, such as, for example, iodometry.
  • the time for the reaction between the peroxodisulfuryl difluoride and the polymer is generally between about 1 and about 100 hours, preferably between about 10 and about 70 hours.
  • the peroxodisulfuryl difluoride is prepared analogously to the method described in the "in-cell” process.
  • the reaction with the polymer is, however, then carried out in another reaction vessel.
  • the peroxodisulfuryl difluoride can then either remain in the electrolyte liquid--the reaction then takes place in the same medium as in the "in-cell” process--or the peroxodisulfuryl difluoride is isolated from the electrolyte by customary methods (such as, for example, by distillation) and mixed with one of the fluorinated solvents mentioned above.
  • An approximately 3-molar to 5-molar solution of peroxodisulfuryl difluoride is preferred for this; it is also possible, however, to keep the proportion of solvent even lower or to dispense with the solvent altogether.
  • the liquid phase is first separated from the polymer, which can be effected by methods known for this purpose (for example removal by distillation, filtration or decanting). Electrolytic phases which have been separated off in this manner can be re-used for a further batch without difficulty, as can also fluorosulfonic acid which has been recovered by distillation.
  • the latter is dried, for example in a stream of inert gas or under reduced pressure.
  • Polymers carrying fluorosulfato groups in the side chains are obtained in this manner.
  • the conversion i.e. the number of fluorosulfato groups introduced, relative to the number of hydrogen atoms initially present, can be varied within wide limits; it is normally between about 10 and about 98%, preferably between about 80 and 98%. If all the side chain end groups --CHFX in the starting polymers are not fluorosulfated, a fraction of the said side chain end groups in the polymer of course remains unaltered, but this does not, as might be expected, interfere with further processing in any way.
  • reaction stage (b) of the process according to the invention can be processed further without difficulty in accordance with reaction stage (b) of the process according to the invention to give the corresponding fluorocarbon polymers carrying carboxyl groups.
  • the methods used here are at least in part known per se.
  • the treatment is carried out at an elevated temperature, if necessary in a pressure-resistant vessel.
  • the polymers containing the ester groups thus formed as side chain end groups are then subjected to an acid or alkaline saponification in a customary manner in order to convert the esters into the free carboxyl groups.
  • the free carboxyl groups are formed in acid saponification, while in alkaline saponification the carboxyl groups are produced in the form of a salt.
  • the --CF 2 OSO 2 F groups in the fluorosulfato compounds obtained in reaction stage (a) of the process according to the invention can also be directly converted into the carboxyl groups in the free form or in the form of a salt by means of water, if appropriate in the presence of a solvent and/or bases. This can be effected in a very simple manner, for example by stirring the fluorosulfato product in water and subsequently isolating it and drying it.
  • Solvents such as, for example, alcohols or ethers
  • bases such as, for example, alkali metal hydroxide solutions
  • the carboxyl group is then produced in the form of a salt, depending on the amount of bases present.
  • aprotic nitrogen bases which can be used here are triethylamine, 1,4-diazabicyclo[2.2.0]octane or 1,8-diazabicyclo[5.4.0]undec-7-ene.
  • the catalyst is preferably employed in an amount of about 1 to 50 mole % relative to the fluorosulfato compound to be decomposed.
  • reaction temperatures are between about -40° and +120° C.
  • This reaction is preferably carried out in inert, aprotic solvents, such as, for example, ethers or nitriles.
  • the process according to the invention constitutes a route to fluorocarbon polymers containing carboxyl groups which is advantageous and represents an advance. This route is made possible via the fluorosulfato compounds formed in the course thereof as intermediate products.
  • the electrolysis cell comprises a laboratory scale glass cylindrical cell of diameter 110 mm and height 250 mm, equipped with a cooling jacket.
  • the base of the vessel is formed by the plate-shaped anode composed of vitreous carbon, 3 mm thick.
  • the cathode is formed by a rod of vitreous carbon, 4 mm thick, which hangs centrally in the cell, fastened to the lid and stops approx. 40 mm above the anode. Down to the bottom length of 35 mm, which remains free, the cathode rod is encased in PTFE tubing. The resulting ratio of anode/cathode surface is approx. 21.
  • the electrolyte is prepared by adding 1,400 g of freshly distilled fluorosulfonic acid to 29.2 g (0.5 mole) of powdered sodium chloride, and the hydrogen chloride formed is stripped off continuously by means of dry nitrogen gas.
  • the carbomethoxy groups are saponified in the customary manner.
  • 1,500 g of electrolyte are electrolyzed for 40 hours at 5 A and a temperature of approx. 10°-20° C., without the addition of polymer powder, the cell voltage being approx. 15 V.
  • the electrolyte is then about 1-molar in peroxodisulfuryl difluoride, as determined by iodometry, and 150 g of finely powdered copolymer formed from 75 mole % of tetrafluoroethylene and 25 mole % of ⁇ -H-perfluoro-(propyl vinyl ether) are added. The mixture is stirred vigorously at 25° C.
  • Frigen F 113 and 800 g of ⁇ -H-perfluoropropyl vinyl ether HCF 2 --CF 2 --CF 2 --O--CF ⁇ CF 2 are placed in a 4,000 ml enamelled kettle, equipped with a paddle stirrer.
  • the vessel is flushed three times with nitrogen and three times with tetrafluoroethylene CF 2 ⁇ CF 2 , tetrafluoroethylene is injected to a pressure of 4 bar and the reaction is started at 40° C. by means of 1.5 g of bis-perfluoropropionyl peroxide. 700 g of tetrafluoroethylene are then introduced in the course of 90 minutes at a constant temperature and pressure.
  • 2,000 ml of Frigen F 113 and 1,200 g of ⁇ -H-perfluoropropyl vinyl ether are put into a 4,000 ml enamelled kettle, equipped with a paddle stirrer.
  • the vessel is flushed 3 times with nitrogen and 3 times with tetrafluoroethylene, tetrafluoroethylene is injected to a pressure of 4 bar and the reaction is started at 40° C. by means of 2 g of bis-perfluoropropionyl peroxide.
  • 550 g of tetrafluoroethylene are then introduced in the course of 120 minutes at a constant temperature and pressure.
  • the polymer has a melt index value of 2 g/10 minutes at 250° C. and a loading of 5 kg.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US06/467,179 1982-02-27 1983-02-16 Process for the preparation of fluorocarbon polymers containing carboxyl groups, and certain starting materials required for this, and the fluoro-sulfato compounds formed as intermediate products in the process Expired - Fee Related US4471076A (en)

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DE3207142 1982-02-27
DE3207142 1982-02-27
DE19823230528 DE3230528A1 (de) 1982-02-27 1982-08-17 Verfahren zur herstellung von carboxylgruppen enthaltenden fluorkohlenstoffpolymerisaten sowie einige ausgangsstoffe hierfuer und die bei dem verfahren als zwischenprodukte auftretenden fluorsulfatoverbindungen
DE3230528 1982-08-17

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4604172A (en) * 1984-08-08 1986-08-05 Hoechst Aktiengesellschaft Process for the electrolysis of sodium chloride
US4981932A (en) * 1984-07-13 1991-01-01 Atochem Fluorated ionic polymer, method for its preparation and membranes
US5137999A (en) * 1987-11-20 1992-08-11 Allied-Signal Inc. Copolymerization of vinyl acetate and a fluoromonomer in an aqueous medium
US5151477A (en) * 1987-11-20 1992-09-29 Allied-Signal Inc. Copolymerization of vinyl acetate and a fluoromonomer in an aqueous medium
US9991537B2 (en) * 2013-05-07 2018-06-05 University of Chester Redox systems

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2589865B2 (fr) * 1985-06-20 1987-12-24 Atochem Nouveau polymere fluore ionique, son procede de preparation et les membranes d'electrolyse formees a partir de ce polymere
ITMI20012744A1 (it) 2001-12-21 2003-06-21 Ausimont Spa Processo di polimerizzazione di monomeri solfonici
ITMI20012746A1 (it) * 2001-12-21 2003-06-21 Ausimont Spa Ionomeri fluorurati
GB2393726A (en) * 2002-08-21 2004-04-07 Regenesys Tech Ltd Ion exchange membranes formed from hydrolysed polymers

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US3528954A (en) * 1967-10-30 1970-09-15 Du Pont Process for homopolymerization of tetrafluoroethylene and copolymerization of same with fluoro co-monomers in the solvent 1,1,2 - trichloro - 1,2,2 - trifluoroethane
US3882093A (en) * 1974-01-02 1975-05-06 Du Pont Sulfonyl-containing fluorocarbon vinyl ethers and ion exchange membrane formed therefrom
US4200711A (en) * 1977-04-25 1980-04-29 Tokuyama Soda Kabushiki Kaisha Process for preparing fluorine-containing polymers having carboxyl groups

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US4267364A (en) * 1977-04-20 1981-05-12 E. I. Dupont De Nemours And Company Fluorinated ion exchange polymer containing carboxylic groups, process for making same, and film and membrane thereof
GB2123812B (en) * 1979-05-31 1984-07-18 Asahi Chemical Ind Fluorinated carboxylic acids and derivatives their production and their use to produce fluorinated acid fluorides

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US3528954A (en) * 1967-10-30 1970-09-15 Du Pont Process for homopolymerization of tetrafluoroethylene and copolymerization of same with fluoro co-monomers in the solvent 1,1,2 - trichloro - 1,2,2 - trifluoroethane
US3882093A (en) * 1974-01-02 1975-05-06 Du Pont Sulfonyl-containing fluorocarbon vinyl ethers and ion exchange membrane formed therefrom
US4200711A (en) * 1977-04-25 1980-04-29 Tokuyama Soda Kabushiki Kaisha Process for preparing fluorine-containing polymers having carboxyl groups

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Kirchmeier et al, Inorg. Chemistry, 12:2886 (1973), of record, pp. 2888 2890 only. *
Kirchmeier et al, Inorg. Chemistry, 12:2886 (1973), of record, pp. 2888-2890 only.
Krespan, J. Fluorine Chem. 2:173 180 (1972/73). *
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4981932A (en) * 1984-07-13 1991-01-01 Atochem Fluorated ionic polymer, method for its preparation and membranes
US4604172A (en) * 1984-08-08 1986-08-05 Hoechst Aktiengesellschaft Process for the electrolysis of sodium chloride
US5137999A (en) * 1987-11-20 1992-08-11 Allied-Signal Inc. Copolymerization of vinyl acetate and a fluoromonomer in an aqueous medium
US5151477A (en) * 1987-11-20 1992-09-29 Allied-Signal Inc. Copolymerization of vinyl acetate and a fluoromonomer in an aqueous medium
US9991537B2 (en) * 2013-05-07 2018-06-05 University of Chester Redox systems

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EP0088285B1 (fr) 1987-10-28
CA1231198A (fr) 1988-01-05
EP0088285A2 (fr) 1983-09-14
DE3230528A1 (de) 1983-09-15
EP0088285A3 (en) 1985-07-10
DE3374200D1 (en) 1987-12-03

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